When various light is irradiated at a substance, an absorption spectrum, a scattered light spectrum and the like are obtained. Conventionally, the spectrum analysis method which measures and utilizes the absorption spectrum, the scattered spectrum, and the like is put in practical use in order to analyze the molecular structure of the substance.
For example, when an infrared ray is emitted to a certain molecule and the wavelength thereof is varied continuously, the infrared ray of the same frequency as the natural frequency of the molecule is absorbed, and a near infrared and infrared absorption spectra (it is sometimes referred to as an infrared spectrum hereafter) corresponding to the molecular structure are obtained. Thus, a method in which the infrared spectrum obtained by emitting an infrared ray to a sample is measured in order to analyze the molecular structure thereof is called infrared absorption spectrum analysis method.
Moreover, when light is emitted to a substance, a strong elastic scattering light which has the same frequency as that of the incident light, and a very weak inelastic scattering light which has the frequency slightly deviated from the frequency of the incident light are scattered. Among these, the Raman scattered light, which is scattered by the vibrating atom and ion in the substrate, is included in the inelastic scattering light. Thus, a method in which a spectrum of the Raman scattered light (it is sometimes referred to as a Raman spectrum hereafter) obtained by irradiating light (especially laser beam) to a sample is measured in order to analyze the molecular structure thereof is called Raman absorption spectrum analysis method.
In these spectrum analysis methods, a substance to be analyzed is prepared as a sample for measurement; the measurement of the spectrum by emitting light to the sample is generally carried out in the condition of atmospheric pressure and room temperature (in ordinary temperature and ordinary pressure condition).
Specifically, a technique which measures an infrared spectrum while heating a sample, such as the heating diffuse reflection method, that is one of the infrared absorption spectrum methods, is known (for example, “Chemical experiment lecture 6. Spectroscopy 1.4th Edition”, the Chemical Society of Japan, Maruzen, published on July 25, Heisei 3 (1991), pp. 230–237, etc.).
According to this reference, an infrared spectrophotometer called diffuse reflectance spectroscopy (DRS) is used, and a powdered material obtained by mixing a substance (solid) to be measured and potassium bromide (KBr) in an equal amount is used as a sample in the heating diffuse reflection method. Infrared light is emitted to the powdered sample, reflection and refraction (transmission) are repeated while varying the depth of penetration, and thereby diffuse reflection phenomenon in which the infrared light is reflected in various directions take place; and the infrared spectrum is measured efficiently by making use of this phenomenon.
Further, in this reference, it is described that, although the measurement in a condition of ordinary temperature and ordinary pressure conditions is common for the heating diffuse reflection method, an infrared spectrum is sometimes measured in a vacuum and heating condition in order to make use in analysis of a compound absorbed on a surface of a catalyst, in the case of infrared spectrum measurement in the field of the catalyst, and that, in such case, a vacuum heating type measurement cell different from an ordinary measurement cell is used in the spectrum measurement chamber of DRS. However, for this method, the target of measurement described in the reference is solid and there is no description how to practically apply heat to a liquid sample. Additionally, what described in the reference is a configuration equipped to the fixed and specific apparatus and there is no description of a contrivance which can be applied to various spectrophotometers by allowing adjust the position of a sample holder to various directions, so as to measure more precise spectrum.
Furthermore, a technology which is called as near infrared optical fiber analysis method in reaction and process controls and in which light is brought from a spectrometer to the site of the sample by means of an appropriate optical fiber, a transmission or reflection light by the sample is brought back to the spectrometer and measurement is carried out. (For example, “Near infrared spectroscopy,” Measurement Series 32 by Japan Society of Spectroscopy, ed. by Y. Ozaki, S. Kawada, et al., published by Academy Publication Center, 1st edition, May 20, 1996, 2nd edition, Nov. 30, 1998, pp. 148–156, etc.)
Although a sample is placed in a sample chamber of a spectrometer and the spectrum is measured for the ordinary spectrometric analysis method, FIG. 4.3.13 in page 150 in this reference describes a method in which light is brought from a spectrometer to the site of the sample by appropriate optical fiber, a transmission or reflection light from the sample is returned to the spectrometer and measurement is carried out and in which a reaction solution is lead from a reaction container cooled with water to the cell through a quartz bypass. Although there is described a method which tracks a polymerization reaction of methyl methacrylate (MMA) while cooled with water, description about the spectrum measurement with heating, the possibility of heating or specific apparatus or structure for heating is not shown. Moreover, the measurement method described in the publication relates to the technique in which light is brought from a spectrometer to the site of the sample by the optical fiber, a transmission or reflection light from the sample is returned to the spectrometer and measurement is carried out; however, a description which specifically suggests a sample holder for spectrum measurement which can be installed in a measurement chamber of the various spectrophotometer and which comprises longitudinal hole for holding a liquid sample, a mechanism controlling the temperature of the liquid sample and a position adjusting means which is to move the position of the holder to be adjusted to the light path of spectrum is not found.
Japanese Patent Publication Hei-01-170843 (pages 1 and 4–6) discloses a thermal analysis/microspectrometry and an apparatus therefor carrying out the thermal analysis and spectrum measurement simultaneously by an optical microscope, which comprises placing a sample on a stage of the microscope, irradiating an infrared ray to reach to the sample from a light source of an infrared spectrophotometer, irradiating an infrared ray transmitted the sample to reach to the infrared spectrophotometer through object lens and aperture of the microscope, detecting light intensity of specific wavelength by the infrared spectrophotometer while varying the temperature of the sample, and measuring an infrared spectrum of the micro-region of the sample at the temperature when light intensity of the specific wavelength changes abruptly or at the temperature before and after that.
The apparatus disclosed in Japanese Patent Publication Hei-01-170843 is common to the present invention in that this apparatus analyzes a molecular structure relation through changes of the spectrum condition of the functional group of the sample by heating the sample; however, this apparatus is one to observe changes in physical properties upon heating of the sample in solid state by the microscope. Specifically, this apparatus is one which macroscopically analyzes phase changes of the sample with changing the temperature of the sample placed on the stage of the microscope and carries out the microscopic observation and infrared spectrum observation simultaneously to thereby captures changes in chemical structure or changes of spatial distribution in micro-scale. However, the object of measurement in the present invention is a liquid sample so that the object of measurement originally differs from that of the reference. The technology disclosed in the reference is the attachment for the microscopic apparatus and has no relation with the present invention. There is no description suggesting the possibility that the similar technology can be applied to the spectrophotometer as disclosed in the present invention.
Japanese Patent Publication Hei-06-242005 (pages 1 and 3) discloses a measuring apparatus which is provided with an internal reflection element penetrated disposed in the center of a container which is a cell or the like, and in which curable resin is held into a cell chamber having windows in front of and behind the internal reflection element and the resin is cured while emitting ultraviolet ray or the like from the window, and, simultaneously, infrared ray is irradiated from a part of the internal reflection element and infrared spectrophotometric absorbance spread by total-reflecting in the internal reflection element is measured. This technology relates to the apparatus which detects the reaction proceeding state of the resin attaching to the internal reflection element by measuring the reflection spectrum from the surface of the internal reflection element of the infrared spectrum.
The technology disclosed in Japanese Kokai Publication Hei-6-242005 is not a technology for spectrum measurement under the condition in which the temperature of a liquid sample is controlled, but it is one of special equipments for observing behavior of curing reaction of the curable resin be attaching to the internal reflection element, in which curing is initiated by heating or by ultraviolet by irradiating infrared spectrum of internal resin to the internal reflection element. The internal reflection element is specifically a prism, and into the cell chamber capable of being inserted with the prism, liquid resin sample is held into the cell and cured, and curing state is observed. However, in order to precisely observe the curing state of the resin by measuring the spectrum, the sensitivity is not enough with this measurement apparatus.
In Japanese Kokai Publication Hei-6-242005, since it only discloses the technology to introduce the light for spectrum measurement to the inside of the liquid resin sample by using the prism, a position adjusting means which can adjust the position of an introducing path of the measuring light in order to apply to the various spectrum measuring equipment is not disclosed or the necessity thereof is not disclosed. A holding block configuration for adjusting the temperature of the liquid sample is not disclosed neither. Therefore, it is a different technology from the present invention.
As the whole, the technology disclosed in Japanese Kokai Publication Hei-6-242005 is one of methods to measure the curing behavior of the resin by the infrared ray and is a method to measure an infrared spectrum by introducing the infrared ray to the internal of the liquid sample by using the prism. This technology is a different technology from the present invention, which is an object of the present invention, regarding a holding block provided with a temperature controlling device for the liquid sample and a holding block provided with a position adjusting means to be used in an ordinary spectrum measurement equipment such as transmission IR, surface reflection IR, Raman scattering spectrum or the like.
Furthermore, in Japanese Patent Publication Hei-11-304689, it is disclosed a sample holder which comprises a sample holding plane being distributed with multiple number of micro-groove for holding a solid sample and which allows to provide a diffused/reflected light necessary for the measurement from the sample within the sample holding plane. In this technology, the usage of a metal file and the like as the solid sample holding plane of the sample holder is disclosed and it is described that incident light upon the sample holding plane, is detected as a diffused/reflected light from the sample in the plurality of micro-grooves, and the condition of the sample on the metal file is solid such as powder or a very small member. However, there is no description about a member on which a liquid sample is applied to thereby measuring transmission and/or reflection of the sample. Moreover, no reference is available which specifically discloses a sample holder for spectrum measurement for measuring the condition of the liquid sample altered by irradiating a light other than a light for spectrum measurement.